TWI797336B - Photopolymerizable coating composition, article with coating layer, laminated film and paint protection film - Google Patents

Abstract

The present invention provides a coating film that maintains good water repellency and antifouling properties. A photopolymerizable coating composition comprising component (a): urethane (meth)acrylate, and component (b): photopolymerizable (meth)acrylic compounds as photopolymerizable components , with respect to the total amount of the photopolymerizable components, the components ( a) mixed with component (b) comprising component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by the following formula (1) , component (b2): reactive silicone, and component (b3): a photopolymerizable acrylic compound that does not contain a urethane unit and does not have a fluorine atom and a Si atom at the same time.

Description

Photopolymerizable coating composition, article with coating layer, product Laminates and paint protection films

The present invention relates to a coating solution that can be used as a top coat of various articles, especially as a material for laminated films such as paint protection films.

Paint Protection Film (PPF) is a film-like product that can be used in the surface protection of industrial products that can be used outdoors. The basic structure of PPF is a laminate of at least two layers including a base material including a flexible and transparent resin film and an adhesive layer. Moreover, PPF is generally supplied on the market in the state of a laminated film that further has a coating layer for improving the antifouling performance or scratch resistance of the substrate on the side opposite to the adhesive layer of the substrate. , and a release layer is further provided on the side of the adhesive layer opposite to the substrate. When using PPF, first cut the PPF according to the surface of the industrial product to be protected, and make the adhesive layer of the cut PPF closely adhere to the surface of the protection target. Products coated with PPF can protect them from various stimuli from the outside world, such as wind and rain, dust, sand, river water, microorganisms, animals, plants or insects, etc. resulting contamination or damage. Specifically, PPF serves as a so-called buffer to buffer pressure or impact from the outside, or PPF bounces off rainwater or dirt, thereby suppressing the influence of external stimuli on the product itself.

The PPF was originally developed for industrial products that can be used in harsh environments such as airplanes, but it is now widely used as a surface protection member for the body of automobiles and motorcycles. For example, by covering the roof, hood, windshield, doors, and trunk doors of a car with PPF, the body can be protected from bird droppings, dead insects, cat tracks, mischief, luggage removal, etc. that bother drivers. damage caused by flying rocks, etc. Usually, the dirt on the surface of the PPF can be easily removed by washing the surface covered with the PPF with water, so the PPF can be used for a long period of time. The PPF that has been used for a certain period can be detached from the vehicle body and easily replaced with a new PPF.

Due to the popularity of vehicles such as automobiles and motorcycles around the world in recent years, there has been a demand for PPFs that can be used in a wider range of environments, such as colder regions, tropical regions, and dry regions. Furthermore, along with the expansion of the market of PPF, the PPF which is simpler and can be properly constructed even by a worker without special skills has been desired. Therefore, for the PPF in recent years, it is required to be integrated into automobiles, motorcycles, etc. to impart flexibility to change the surface shape, durability to withstand long-term external stimuli, and transparency and smoothness that do not damage the appearance of the product itself. properties, such as good peelability at the time of replacement, etc.

As such PPF, for example, Patent Document 1 describes that, by laminating a base film and an adhesive layer whose surface roughness is controlled, a PPF having excellent adhesion characteristics and suppressed adhesive residue is provided. However, in the above-mentioned PPF, the antifouling layer added to the surface of the base film has not been specifically studied, and there is a problem in practicality for automobiles and motorcycles where appearance is important.

In addition, for example, Patent Document 2 describes a PPF in which a first layer made of polyurethane, a second layer made of thermoplastic polyurethane, and a third layer made of a pressure-sensitive adhesive are sequentially laminated. . However, further improvements in various properties are also required in the PPF.

[Prior art literature]

[Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2016-20079

Patent Document 2: Japanese Patent Application Publication No. 2008-539107

The existing PPF technology leaves room for improvement. As the performance to be improved, the present inventors particularly focused on weather stability, which was not studied in the prior art, that is, maintaining the initial stain resistance and water resistance even after long-term use in a severe outdoor environment. The inventors of the present invention intend to improve the weather resistance stability by changing the coating film material constituting the outermost surface of PPF.

As a result, it was found that an acrylic photopolymerizable coating composition containing two specific fluorine-containing photopolymerizable components provides a coating film (coating layer) exhibiting long-lasting antifouling and water repellency. Furthermore, the present inventors found that a coating layer composed of a cured product of the photopolymerizable coating composition can be used as a laminated film such as PPF. That is, the present invention is as follows.

(Invention 1) A photopolymerizable coating composition comprising component (a): Urethane (meth)acrylate, and component (b): photopolymerizable (meth)acrylic compounds as photopolymerizable components, with respect to the total amount of the photopolymerizable components, the component ( a): 1% by weight to 50% by weight, component (b): 50% by weight to 99% by weight by mixing the component (a) and component (b), The component (b) includes component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by the following formula (1), component (b2): reactive silicon Ketone and component (b3): A photopolymerizable acrylic compound that does not contain a urethane unit and does not have a fluorine atom and a Si atom at the same time.

(In formula (1), R _f ¹ ~ R _f ⁷ are each independently any methylene group that can be substituted by oxygen, straight-chain or branched-chain fluoroalkyl with carbon number 1 ~ 20; at least one hydrogen can be A fluoroaryl group with 6 to 20 carbons substituted by fluorine or trifluoromethyl; or a fluoroarylalkyl group with 7 to 20 carbons in which at least one hydrogen in the aryl group can be substituted by fluorine or trifluoromethyl, A ¹ is a group represented by the following formula (1-1) or formula (1-2))

(In formula (1-1), Y ³ is an alkylene group with 2 to 10 carbons, R ⁶ is hydrogen, a linear alkyl group with 1 to 5 carbons, a branched chain with 3 to 5 carbons Alkyl, or aryl with 6~10 carbons)

(In formula (1-2), Y ⁴ is a single bond or an alkylene group with 1 to 10 carbons)

(Invention 2) The photopolymerizable coating composition according to Invention 1, wherein the component (b1) contains γ-methacryloxygen derived from the following formula (1-3) Structural unit of hepta(trifluoropropyl)-T8-silsesquioxane.

The component (b2) is a polyorganosiloxane compound having a vinyl group at its terminal.

(Invention 3) The photopolymerizable coating composition according to Invention 1, further comprising component (c): a fluorine-based surfactant.

(Invention 4) An article including a coating layer composed of a cured product of the photopolymerizable coating composition according to any one of Inventions 1 to 3.

(Invention 5) A laminated film comprising a coating layer composed of a cured product of the photopolymerizable coating composition according to any one of Inventions 1 to 3, and a coating layer composed of thermoplastic polyurethane. The substrate layer, the adhesive layer made of pressure-sensitive adhesive, and the release layer coated with a fluorine-based or silicone-based release agent are sequentially connected.

(Invention 6) A paint surface protection film using the laminated film according to Invention 5.

The good antifouling and waterproof properties of the coating film (coating layer) obtained from the photopolymerizable coating composition of the present invention last even after long-term outdoor use.

1: coating layer

2: Substrate layer

3: Adhesive layer

4: peeling layer

5:Laminated film

6: Coating surface

7:PPF

FIG. 1 is a diagram schematically showing an example of the laminated film of the present invention.

Fig. 2 is a diagram schematically showing a case where the laminated film of the present invention is used as a PPF.

[1. Photopolymerizable coating composition]

The photocoating composition of the present invention contains the following component (a): urethane (meth)acrylate, and the following component (b): photopolymerizable (meth)acrylic compound as essential components photopolymerizable components. In the photopolymerizable coating composition of the present invention, the above-mentioned component (a) and component (b) may be in a diluted state, or may contain an undiluted polymer.

In the present invention, with respect to the total amount of the photopolymerizable components, a ratio of component (a): 1% by weight to 50% by weight, component (b): 50% by weight to 99% by weight, Preferably, the component (a) and the component (b) are mixed in a ratio of component (a): 1% by weight to 30% by weight, and component (b): 70% by weight to 99% by weight.

[Component (a): Urethane (meth)acrylate]

The urethane (meth)acrylate used as the component (a) is borrowed Oligomerization of reactive (meth)acryl groups at terminals obtained by the reaction of isocyanate compounds, polyols, hydroxyl group-containing (meth)acrylic monomers, and isocyanate group-containing (meth)acrylic monomers A general term for compounds in the form of substances.

The urethane (meth)acrylate usable in the present invention is typically an ultraviolet curable urethane (meth)acrylate, and preferably (i) contains an aliphatic isocyanate compound and/or or an isocyanate compound of an alicyclic isocyanate compound, and one or more polyol compounds selected from (ii) an ester polyol, (iii) an ether polyol, or (iv) a polycarbonate polyol, and (v) ) Urethane (meth)acrylate obtained by reacting a (meth)acrylate compound having a hydroxyl group.

As (i) said aliphatic isocyanate compound, hexamethylene diisocyanate, the isocyanurate modification body of hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc. are mentioned, for example. As said alicyclic isocyanate compound, isophorone diisocyanate, 4,4'- dicyclohexylmethane isocyanate, hydrogenated xylene diisocyanate, etc. are mentioned, for example.

As (ii) said ester type polyol, the ester compound which made diols and dicarboxylic acid react, for example is mentioned. Examples of the diols include 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and 1,3-butanediol , 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, etc. Examples of the dicarboxylic acid include sebacic acid, adipic acid, dimer acid, succinic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, citraconic acid, and the like. Anhydrides of these may be used.

Examples of (iii) ether-based polyols include polyether diols, poly(oxygen oxytetramethylene) glycol, poly(oxybutylene) glycol, etc. Specific examples of the polyether diol include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and propylene-modified polytetramethylene glycol.

Examples of (iv) polycarbonate-based polyols include reaction products of carbonate derivatives and diols. Examples of the carbonate derivatives include diallyl carbonates such as diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. Moreover, the said compound is mentioned as said diols.

Examples of (v) acrylate compounds having a hydroxyl group include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate ) 4-hydroxybutyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like.

In the production of the above-mentioned urethane acrylate, it can be reacted by incorporating an isocyanate compound, a polyol compound, and an acrylate compound having a hydroxyl group as essential constituents together. Alternatively, a (meth)acrylate compound having a hydroxyl group may be reacted with these isocyanate compounds to temporarily produce a prepolymer having excess isocyanate groups, and then the remaining isocyanate groups may be reacted with a polyol compound.

Alternatively, an isocyanate compound and a polyol compound may be reacted to temporarily produce a prepolymer having excess isocyanate groups, and then the remaining isocyanate groups may be reacted with a (meth)acrylate compound having a hydroxyl group. The urethane (meth)acrylate produced by these methods preferably has a polyurethane chain.

In the present invention, commercially available Violet Co., Ltd. of Nippon Synthetic Chemicals Co., Ltd. Hikari UT-5569, AUP-838 manufactured by TOKUSHIKI, RUA-062S, RUA-058SY2 manufactured by Asia Chemical Co., Ltd., RUA-012 manufactured by Asia Industry, RUA-075, P7 manufactured by Kyoeisha Chemical Co., Ltd. 532 et al.

[Component (b): Photopolymerizable (meth)acrylic compounds]

The photopolymerizable coating composition of the present invention contains component (b): a photopolymerizable (meth)acrylic compound as a component photocopolymerizable with the above-mentioned component (a). The component (b) includes component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by the following formula (1), component (b2): reactive silicon Ketone and component (b3): A photopolymerizable acrylic compound that does not contain a urethane unit and does not have a fluorine atom and a Si atom at the same time. The component (b1), component (b2), and component (b3) are mixed in a diluted state or in a state containing an undiluted polymer.

The ratio of each of the component (b1), component (b2), and component (b3) to the component (b) is not particularly limited. Usually, the total amount of the component (b1) and the component (b2) is 0.1% by weight to 10% by weight relative to the total amount of the component (b), preferably 0.5% by weight to 5% by weight. % of the following ways to deploy each component. Moreover, the said component (b2) is combined with respect to the said component (b1) normally 0.1 times or more and 10 times or less, Preferably it is 0.2 times or more and 5 times or less on a mass basis. In the present invention, a synergistic effect can be obtained by using the component (b2) in combination with the above-mentioned component (b1).

[Component (b1): Photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative]

The component (b1) contained in the component (b) of the present invention has a fluorosilsesquioxane structure, and can be generally classified into a random structure, a trapezoidal structure, and a cage structure according to its Si—O—Si skeleton. Among them, a photopolymerizable (meth)acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by the following formula (1) is particularly preferable.

In formula (1), R _f ¹ to R _f ⁷ are each independently any methylene group that can be substituted by oxygen, a straight-chain or branched-chain fluoroalkyl group with 1 to 20 carbons; at least one hydrogen can be A fluoroaryl group with 6 to 20 carbons substituted by fluorine or trifluoromethyl; or a fluoroarylalkyl group with 7 to 20 carbons in which at least one hydrogen in the aryl group can be substituted by fluorine or trifluoromethyl, A ¹ is a group represented by the following formula (1-1) or formula (1-2).

Preferably, R _f ¹ to R _f ⁷ in formula (1) are independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3, 4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecane Hexafluoro-1,1,2,2-tetrahydrododecyl, Pentafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy base) propyl, pentafluorophenylpropyl, pentafluorophenyl or α,α,α-trifluoromethylphenyl.

More preferably, R _f ¹ to R _f ⁷ in formula (1) are independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nine Fluorohexyl.

In formula (1-1), Y ³ is an alkylene group with 2 to 10 carbons, preferably an alkylene group with 2 to 6 carbons, R ⁶ is hydrogen, or a straight chain or branched chain with 1 to 5 carbons chain alkyl, or aryl with 6 to 10 carbons, preferably hydrogen or alkyl with 1 to 3 carbons.

In the formula (1-2), Y ⁴ is a single bond or an alkylene group having 1 to 10 carbon atoms.

The fluorosilsesquioxane derivative (1) can be produced by the following method. First, the silicon compound (2) having a trifunctional hydrolyzable group represented by the following formula (2) is hydrolyzed and polycondensed in an oxygen-containing organic solvent in the presence of an alkali metal hydroxide to produce Compound (3) represented by the following formula (3).

In formula (3), if M is an alkali metal, it will not specifically limit. Examples of the alkali metal include lithium, sodium, potassium, and cesium.

R in formula (2) and formula (3) is independently consistent with a group selected from R _f ¹ to R _f ⁷ of formula (1), and is any carbon that can be substituted by oxygen in methylene A linear or branched fluoroalkyl group with a number of 1 to 20; a fluoroaryl group with a carbon number of 6 to 20 that can be replaced by fluorine or trifluoromethyl; or at least one hydrogen in an aryl group can be replaced by A fluoroarylalkyl group with 7 to 20 carbon atoms substituted by fluorine or trifluoromethyl, and X is a hydrolyzable group.

Preferably, R in formula (2) and formula (3) are independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4 ,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl , Hexafluoro-1,1,2,2-tetrahydrododecyl, Pentafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy ) propyl, pentafluorophenylpropyl, pentafluorophenyl or α,α,α-trifluoromethylphenyl.

More preferably, R in formula (2) are each independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

Next, the fluorosilsesquioxane derivative (1) can be obtained by reacting the compound (4) represented by the following formula (4) with the compound (3).

[chemical 10]

The group X in the formula (4) is a group represented by the above-mentioned formula (1-1) or formula (1-2).

Among the fluorosilsesquioxane derivatives (1), it is preferably γ-methacryloxypropyl hepta(trifluoropropyl)-T8-silsesquioxane represented by the following formula (5): alkyl.

If fluorosilsesquioxane derivatives (1) such as γ-methacryloxypropyl hepta(trifluoropropyl)-T8-silsesquioxane are introduced into the coating layer, the Anti-fouling function of the coating layer. Contained in photopolymerizable (meth)acrylic compounds When the fluorosilsesquioxane derivative (1) is used, it can also be directly mixed with other photopolymerizable (meth)acrylic compounds, or it can be mixed with photopolymerizable (meth)acrylic compounds. Oligomers prepared by crosslinking and/or copolymerizing in advance are mixed with other photopolymerizable acrylic compounds.

Usually, fluorosilsesquioxane derivative (1) is prepared in advance by copolymerizing one or more (meth)acrylate copolymer components selected from monofunctional acrylates, difunctional acrylates, and polyfunctional acrylates. A polymer having a fluorosilsesquioxane derivative (1) unit, the polymer being used as a part of photopolymerizable (meth)acrylic compounds. In this case, the polymer containing the fluorosilsesquioxane derivative (1) unit is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, relative to the photopolymerizable component. deployment.

As the one or more (meth)acrylate-based copolymerization components, generally, compounds called photocurable acrylic monomers, such as (meth)acrylic acid, (meth)acrylate or hydroxyl-containing (meth)acrylic acid monomers, can be used. Monofunctional acrylates such as (poly)alkanediol di(meth)acrylates, polyfunctional acrylates such as pentaerythritol triacrylate, etc., and for these Oligomers obtained by polymerization.

[Component (b2): Reactive Silicone]

The component (b2) contained in the said component (b) of this invention: Reactive silicone is a silicone compound group also called reactive silicone oil, polysiloxane system macromonomer. In the field of polymer synthesis, these are used as raw materials for block copolymers or graft copolymers, and also as reforming materials for molding resins and reforming agents for paints. the ingredients (b2) Improve the surface smoothness of the photopolymerizable coating composition of the present invention.

The component (b2) is preferably a polyorganosiloxane compound having a vinyl group at the end, and more preferably a polydimethylsiloxane macromonomer having a methacryl group at the end.

[Component (b3): A photopolymerizable acrylic compound that does not contain a urethane unit and does not have both a fluorine atom and a Si atom]

In the photopolymerizable coating composition of the present invention, the component (b3): a photopolymerizable acrylic compound that does not contain a urethane unit and does not have a fluorine atom and a Si atom at the same time as the component (a) , a crosslinking agent or a copolymerizable monomer for photopolymerizing at least one of the component (b1) and the component (b2). The component (b3) contributes to the extension of the polymer chain during hardening of the photopolymerizable coating composition of the present invention. The resin component mainly composed of the component (b3) contained in the curing contributes to the strength of the coating film (coating layer) formed in the curing. The component (b3) can be selected from a photopolymerizable acrylic compound or various compounds and products available as a solution containing the same, and the type is not limited.

The component (b3) may be supplied to the photopolymerizable coating composition of the present invention in the form of mixing one or more selected from the component (a), component (b1) and component (b2) in advance. A copolymer obtained by reacting at least a part of the component (b3) with one or more selected from the component (a), component (b1), and component (b2) can also be supplied to the photopolymerizable coating composition.

[Component (c): Fluorinated Surfactant]

The photopolymerizable coating composition of the present invention may further contain component (c): fluorine-based Surfactant. The component (c) is a monomer or oligomer having a fluorine atom and a photopolymerizable unsaturated group in its chemical structure, and is referred to as a fluorine-based additive, a fluorine-based surfactant, a fluorine-based A group of materials such as surface modifiers. In this specification, for the sake of convenience, the component (c) is described as a "fluorine-based surfactant" which is one of general names.

As the component (c), it is preferable to use various organic solvents (such as ether solvents, ester solvents, ketone solvents, and alcohol solvents) that do not cause component separation in the photopolymerizable coating composition of the present invention. etc.) in the highly soluble non-ionic components. In addition, the component (c) is preferably a component containing 0.01% by weight to 80% by weight of fluorine.

A preferable component (c) is a perfluoropolyether compound having a perfluoropolyether skeleton and having a photopolymerizable unsaturated group at one or both ends thereof. The perfluoropolyether skeleton represents, for example, a repeating structure such as -(O-CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ )-, or -(O-CF ₂ C(CF ₃ )F)-. The photopolymerizable unsaturated group is not particularly limited, and examples thereof include groups such as (meth)acryl, (meth)acryloxy, vinyl, and allyl, and are combined with the component (a) or From the viewpoint of the reactivity of the component (b), a (meth)acryl group is preferred.

As the component (c), for example, "Megafac (registered trademark) RS-75" (manufactured by DIC Co., Ltd.), "KY-1203" (manufactured by Shin-Etsu Chemical Co., Ltd.), "Fluorine FLUOROLINK AD1700", "FLUOROLINK MD700" (manufactured by Solvay Solexis), "OPTOOL DAC-HP" (Daikin Chemical Industry Co., Ltd.), "CN4000" (manufactured by Sartomer), etc.

With respect to the photopolymerizable component, the photopolymerizable coating composition of the present invention can generally contain 0.1% by weight or more and 10% by weight or less, preferably 0.5% by weight or more and 5% by weight or less of the component (c ).

[2. Polymerization initiator]

As the polymerization initiator usable for hardening the photopolymerizable coating composition of the present invention, those that are marketed under the name of the photopolymerization initiator can be used without limitation. As the photopolymerization initiator, polymers of hydroxy ketones such as {2-hydroxy-2-methyl-1-phenylpropanone}, 1-hydroxydicyclohexyl phenyl ketone, 2-hydroxy- 2-Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-{4(2-hydroxyethoxy) Phenyl}2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6 trimethylbenzyl Acyl)phenylphosphine oxide, etc.

[3. Additives]

Additives such as antioxidants, weather-resistant stabilizers, toners, thinners, etc. that are usually formulated in paint or film materials can be formulated in the photopolymerizable coating composition of the present invention. It will not restrict|limit if the compounding quantity is the range which does not lower the function of the photopolymerizable coating composition of this invention.

[4. Utilization of photopolymerizable coating composition]

Hardening is performed by applying the photopolymerizable coating composition of the present invention to the surface of various articles. When dry, it can form an anti-fouling effect on the surface of the article. Waterproof film (coating layer). The articles that can form the coating layer are not particularly limited, in particular, they can be simply A laminated film is advantageous in terms of simply applying the liquid photopolymerizable coating composition of the present invention. Antifouling is required in the laminated film. PPF having a water-repellent function is particularly useful as an article using the coating layer.

Hereinafter, the laminated film provided with the said coating layer is demonstrated in detail.

[coating layer]

The coating layer constituting the laminated film of the present invention contains a polymer obtained by curing the photopolymerizable coating composition on the substrate layer in the presence of a polymerization initiator. The thickness of the coating layer is usually 1 μm to 100 μm, preferably 2 μm to 50 μm, more preferably 3 μm to 30 μm. The structure of the polymer constituting the coating layer is complex and cannot be represented by a single structural unit or a uniform structural formula. The polymer constituting the coating layer in the present invention is defined by the photopolymerizable compound contained in the photopolymerizable coating composition.

[Substrate layer]

As the base material layer constituting the laminated film of the present invention, it is desirable to use a film formed of a thermoplastic resin. Examples of thermoplastic resins include polyurethane-based resins, polyester-based resins, acetate-based resins, polyether-based resins, polycarbonate-based resins, polyamide-based resins, and polyimide-based resins. Resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyacrylate resin, polyphenylene sulfide Resins such as ether-based resins and norbornene-based resins. Specifically, thermoplastic polyurethane, polycaprolactone (polycaprolactone, PCL), acrylic polymer, polyester, polyacrylonitrile, polyether ketone, polystyrene, polyvinyl acetate or the like are preferred. some derivatives. can be used alone These resins may be used in combination of a plurality of resins.

A particularly preferred substrate layer is thermoplastic polyurethane. Examples of thermoplastic polyurethanes include ArgoGuard (registered trademark) 49510 manufactured by SWM, ArgoGuard (registered trademark) 49510-DV, Japan Matai ) manufactured by Esmer URSPX86, Esmer URSPX93, Esmer URSPX98, DUS202, DUS213, DUS235, DUS501, DUS601, DUS605, DUS614 manufactured by SHEEDOM, DUS203, DUS220, DUS701, XUS2086, XUS2098, DUS451, DUS450, Unigrand XN2001, XN2002, XN2004 manufactured by Japan unipolymer company. Among them, as the polyhydroxy compound, polycaprolactone-based thermoplastic polyurethane using polycaprolactone polyol, polycarbonate-based thermoplastic polyurethane using polycarbonate polyol is preferable. Polyester, polyether thermoplastic polyurethane using polyether polyol.

The thickness of the substrate layer in the present invention is not particularly limited, and is usually 25 μm to 300 μm, preferably 100 μm to 200 μm.

[adhesive layer]

The adhesive layer constituting the laminated film of the present invention contains a pressure-sensitive adhesive. As the pressure-sensitive adhesive used in the present invention, if it exhibits adhesiveness at the construction temperature of PPF, that is, at a temperature of about 20°C to about 30°C, it can be used for molding including thermoplastic polyurethane-based materials. If there are any successors between articles and glass or metal, plastic, paper, etc., the known ones can be used without restriction. As the pressure-sensitive adhesive, commercially available acrylic Acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, preferably acrylic pressure-sensitive adhesives can be used. The thickness of the adhesive layer is not particularly limited, but is usually about 10 μm to 200 μm.

[peeling layer]

It is preferable that a peeling layer is further laminated|stacked on the adhesive layer which comprises the laminated film of this invention. As the material of the release layer, known release materials can be used without limitation, for example, resin films such as polyester resins or polyolefin resins, cellophane, thin cellophane, or fluorine-based or silicone-based release agents can be used for the release layer. Those who carry out surface coating. The thickness of the release layer is not particularly limited, but is usually about 20 μm to 200 μm.

[The protective layer]

In the laminated film of the present invention, the outer surface of the coating layer can be covered with a protective layer according to the form of storage, transportation, and sale. The material of the protective layer is not limited, and generally available plastic films such as polyethylene films or peeled papers can be appropriately selected.

[Manufacture of laminated film]

The manufacturing method of the laminated film of the present invention can be used without limitation for the formation of each layer. layered method. For example, when the laminated film of the present invention has a release layer and a protective layer, the laminated film of the present invention can be produced through the following steps.

First, an adhesive layer is formed on the peeled surface of the peeling layer. Then, the open surface of the formed adhesive layer is brought into close contact with one surface of the base material layer to manufacture a laminate in which the base material layer, the adhesive layer, and the release layer are sequentially contacted. Next, the photopolymerizable coating composition is coated on the released surface of the substrate layer of the obtained laminate. The finished product is irradiated with ultraviolet rays on the coated surface to harden the photopolymerizable coating composition. After curing, a laminated film in which the coating layer, substrate layer, adhesive layer, and peeling layer are sequentially connected can be obtained. Furthermore, the open surface of the coating layer was covered with a protective film. In this way, a laminated film in which the protective layer, the coating layer, the base material layer, the adhesive layer, and the peeling layer are sequentially connected can be obtained. The obtained laminated film is suitably cut, wound, and packaged.

[PPF]

The laminated film of the present invention completed in the above manner can be cut, loaded or rolled up in an appropriate length unit, and can be utilized as a PPF. When constructing PPF, the laminated film of the present invention is cut into a shape suitable for the shape or size of the painted surface, and the cut laminated film is unfolded with moderate force to make the adhesive layer adhere to the painted surface.

In the laminated film of the present invention, the coating layer excellent in strength, smoothness, water repellency, and oil repellency has the function of alleviating external stimulation to the construction surface. On the other hand, the flexible base layer is in close contact with the painted surface via the adhesive layer. After a certain period of use, the laminated film can be removed without damaging the surface of the painted surface.

[Example]

[Manufacture of a polymer comprising γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane unit as an example of component (b1)]

First, γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane was synthesized by the following procedure. Put trifluoropropyltrimethoxysilane (100g), tetrahydrofuran (tetrahydrofuran, THF) (500mL), deionized water (10.5 g), and sodium hydroxide (7.9g), one side utilizes magnetic stirrer to stir, one side by oil bath It was heated from room temperature to the reflux temperature of THF. Stirring was continued for 5 hours from reflux to complete the reaction. Thereafter, the flask was lifted from the oil bath, and after standing overnight at room temperature, it was placed in the oil bath again, and heated and concentrated under constant pressure until solids were precipitated.

The precipitated product was collected by filtration using a pressure filter equipped with a membrane filter having a pore size of 0.5 μm. Next, the obtained solid was washed once with THF, and dried at 80° C. for 3 hours with a reduced-pressure dryer to obtain 74 g of a colorless powdery solid.

The obtained solid (65 g), dichloromethane (491 g), and triethylamine (8.1 g) were charged into a four-neck flask with an inner volume of 1 L equipped with a reflux cooler, a thermometer, and a dropping funnel, and cooled in an ice bath. until 3°C. Next, γ-methacryloxypropyl trichlorosilane (21.2 g) was added, and after confirming that heat generation had ceased, it was lifted from an ice bath, and aged overnight at room temperature in this state. After washing three times with ion-exchanged water, the dichloromethane layer was dehydrated with anhydrous magnesium sulfate, and the magnesium sulfate was removed by filtration. Concentrate with a rotary evaporator until a viscous solid precipitates, add 260 g of methanol, and stir until it becomes powdery. The powder was filtered using a pressure filter equipped with a filter paper of 5 μm, and dried at 65° C. for 3 hours with a reduced-pressure drier to obtain 41.5 g of a colorless powdery solid. Gel Permeation Chromatography (GPC) and ¹ H-nuclear magnetic resonance (nuclear magnetic resonance, NMR) measurements were performed on the obtained solid, and it was confirmed that γ-methacrylamide represented by the following formula (5) Generation of oxypropylhepta(trifluoropropyl)-T8-silsesquioxane (5).

[chemical 12]

Next, a polymer comprising γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units was synthesized using the following procedure.

Add the compound 5 (25 g), Serapure (Silaplane) FM0721 (6.3 g, manufactured by JNC (stock)), methyl 2-Hydroxyethyl acrylate (18.8g), methyl methacrylate (12.5g), methyl ethyl ketone (62g), refluxed for 15 minutes using an oil bath. After degassing, the solution which melt|dissolved azobisisobutyronitrile (0.48g) and thioglycolic acid (0.054g) in methyl ethyl ketone (4.8g) was injected|thrown-in, and superposition|polymerization started. Three hours after the start of the polymerization, azobisisobutyronitrile (0.48 g) was dissolved in methyl ethyl ketone (4.3 g) and added to obtain a solution of a copolymer obtained by aging for 5 hours. Furthermore, as a polymerization initiator, p-methoxyphenol (0.16 g) and dibutyltin dilaurate (0.15 g, manufactured by Showa Denko Co., Ltd.) were dissolved in methyl ethyl ketone (1.5 g) and added , using a dropping funnel to drop Karenz (Karenz) AOI (26.4g) in such a way that the liquid temperature changed from 35°C to 50°C, and after the dropwise addition, it was at 45°C. Cake for 3 hours.

Thereafter, after adding methanol (9g) and treating it, p-methoxyl was further added Phenol (0.16 g) was diluted with methyl isobutyl ketone (107.3 g) to obtain a 30% by weight solution of the target polymer (A-1).

The obtained polymer (A-1) had a weight average molecular weight: Mw of 42,000, and a polydispersity index: Mw/Mn of 1.9. Weight-average molecular weight and polydispersity index use gel permeation chromatography (GPC (Gel Permeation Chromatography), model: Alansi (Alliance) 2695, manufactured by Waters (waters), column: Sodex (Shodex) GPC KF-804L×2 pieces (serial), guard column: KF-G) were measured. It was confirmed by GPC analysis that the obtained polymer (A-1) contained γ-methacryloxypropyl hepta(trifluoropropyl)-T8-silsesquioxane unit and had acryl group in the side chain of polymers.

[Manufacture of photopolymerizable coating composition]

The materials were mixed and stirred in the compositions shown in Table 1 to manufacture the photopolymerizable coating composition of the present invention and the photopolymerizable coating composition for comparison. The materials used are shown below.

(ingredient (a))

． P7-532: Urethane acrylate product manufactured by Kyoeisha Chemical Co., Ltd.

(ingredient (b1))

． XUA008: Polymer (A-1) produced by the method. It is a polymer containing γ-methacryloxypropyl hepta(trifluoropropyl)-T8-silsesquioxane unit and having acryl group in the side chain.

(ingredient (b2))

． FM7711: Silaplane (registered trademark) manufactured by JNC. A polydimethylsiloxane macromonomer having methacryloxy groups at both ends with an average number molecular weight of 1,000.

． FM7725: Silaplane (registered trademark) manufactured by JNC. A polydimethylsiloxane macromonomer having methacryloxy groups at both ends with an average number molecular weight of 10,000.

(ingredient (b3))

． M309: Aronix (registered trademark) manufactured by Toa Gosei. Trimethylolpropane Triacrylate.

． DPCA-120: KAYARAD manufactured by Nippon Kayaku. Caprolactone modified dipentaerythritol hexaacrylate.

． A-HD-N: A product made by Shin-Nakamura Chemical. 1,6-Hexanediol diacrylate.

(ingredient (c))

． RS-75: DIC fluorine additive Megafac (registered trademark). Contains fluorine-containing groups. Hydrophilic base. lipophilic base. Oligomers of UV reactive groups.

(other ingredients)

． Irgacure 127 (not described in Table 1): A photopolymerization initiator product manufactured by BASF. It was prepared so as to become 7% by weight of the total amount of the photopolymerizable coating composition.

[Manufacture of laminated film]

A thermoplastic polyurethane film "ArgoGuard (registered trademark) 49510" (thickness: about 152 μm) manufactured by SWM was used as the base material layer.

In addition, it is commercially available as a release layer coating with a release treatment using silicone resin. Dry acrylic pressure-sensitive adhesive at 120°C for 5 minutes. In this way, an adhesive layer with a thickness of 40 μm was formed on one side of the release layer.

Next, use a rubber roller to press the open surface of the adhesive layer to the base material layer, and maintain at 45° C. for one day. In this way, a laminated film in which the substrate layer, the adhesive layer, and the peeling layer are sequentially connected is obtained.

The photopolymerizable coating composition produced using the above material was coated on the open surface of the substrate layer with a Meyer bar, and dried at 80° C. for 3 minutes. Thereafter, the photopolymerizable coating composition was cured at a cumulative light intensity of 500 mJ/cm ² using a conveyor curing unit (manufactured by Heraeus) mounted on a Fusion UV lamp. A coating layer with a thickness of 4 μm was formed on the base layer. A laminated film 5 in which the coating layer 1, the substrate layer 2, the adhesive layer 3, and the peeling layer 4 are sequentially connected can be obtained.

[Evaluation of laminated film]

(1) Water contact angle (water resistance)

1.8 μl of distilled water was dropped on the surface of the coating layer of the laminate, and the angle (water contact angle) formed by the droplet of distilled water and the surface of the coating layer of the laminate was measured. As a measuring machine, a contact angle meter, Drop Master 400 (manufactured by Kyowa Interface Science), was used. The measured values were evaluated by the following criteria. The results are shown in Table 1.

． A: The water contact angle is 100 degrees or more. good water resistance

． B: The water contact angle is less than 100 degrees. Poor water resistance.

(2) Coefficient of friction (slidability)

Measurement of the static friction coefficient and dynamic friction coefficient of the surface of the coating layer of the laminate number. As a measuring machine, HEIDON Type 14W manufactured by Shinto Chemical was used. The rubbing conditions were 11 mm in diameter of the indenter, 200 g of load, 300 mm/min of speed, and 50 mm of one-way movement. The results are shown in Table 1.

(3) Squeegee Slidability (Workability)

A 40 mm x 130 mm piece was cut out from the laminated film, the release layer was removed, and a laminated film in which the coating layer, base material layer, and adhesive layer were sequentially connected was prepared. In addition, an aluminum plate (50 mm in width, 150 mm in length, and 1.2 mm in thickness) painted with black paint for automobiles was prepared.

After spraying water on the surface of the adhesive layer of the laminated film and the painted surface 6 of the painted panel (wherein the baby shampoo (babyshampoo) manufactured by Johnson & Johnson is diluted to 10,000 times on a volume basis) , make the adhesive layer of the laminated film come into contact with the painted surface, use a commercially available rubber scraper to remove air bubbles and blisters formed between the laminated film and the painted surface, and press the laminated film to attach the laminated film to the painted surface. plate. The slidability (squeegee slidability) of the laminated film at this time was judged by the following criteria. The results are shown in Table 1.

"+": The scraper slides on the surface of the laminated film, and the laminated film is attached without difficulty.

"-": The scraper is hooked on the surface of the laminated film, or uneven resistance is applied to the scraper, which hinders the adhesion of the laminated film.

As shown in the results in Table 1, in the laminated film in which the coating layer was formed using the photopolymerizable coating composition of the present invention, good water repellency, sliding properties, and workability were obtained. In particular, in the photopolymerizable coating composition of the present invention containing component (c) in addition to component (a) and component (b), extremely good water repellency, sliding properties, and workability can be obtained. On the other hand, in the laminated film of the comparative example which lacked any one of the component (b1) of this invention, or a component (b2), waterproofness and workability were inferior.

[Industrial availability]

The photopolymerizable coating composition of the present invention is used as water repellency. Antifouling coating material and high utilization value. A laminated film having a coating layer using the photopolymerizable coating composition of the present invention has high utility value as PPF 7 . As the target of application of the PPF including the laminated film of the present invention, in addition to vehicles such as automobiles and motorcycles, ships, buildings, electrical products, exhibits, interiors, furniture, factory equipment, industrial equipment, medical equipment, etc. are expected to be widely used. Object.

1: coating layer

2: Substrate layer

3: Adhesive layer

4: peeling layer

5:Laminated film

7:PPF

Claims (6)

A photopolymerizable coating composition comprising component (a): urethane (meth)acrylate, and component (b): photopolymerizable (meth)acrylic compounds as photopolymerizable components , with respect to the total amount of the photopolymerizable components, the components ( a) mixed with component (b) comprising component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by the following formula (1) , component (b2): a polyorganosiloxane compound containing vinyl groups at both ends, and component (b3): a photopolymerizable acrylic compound that does not contain a urethane unit and does not have a fluorine atom and a Si atom at the same time;

In formula (1), R _f ¹ to R _f ⁷ are independently straight-chain or branched fluoroalkyl groups with 1 to 20 carbons, fluoroaryl groups with 6 to 20 carbons, or 7 to 7 carbons. 20 fluoroarylalkyl, any methylene in the fluoroalkyl can be substituted by oxygen; at least one hydrogen of the fluoroaryl can be substituted by fluorine or trifluoromethyl; the fluoroarylalkyl At least one hydrogen in the aryl group can be substituted by fluorine or trifluoromethyl; ^A is a group represented by the following formula (1-1) or formula (1-2),

In formula (1-1), Y ³ is an alkylene group with 2 to 10 carbons, R ⁶ is hydrogen, a linear alkyl with 1 to 5 carbons, a branched chain with 3 to 5 carbons. group, or an aryl group with 6 to 10 carbon atoms,

In the formula (1-2), Y ⁴ is a single bond or an alkylene group having 1 to 10 carbon atoms. The photopolymerizable coating composition as described in claim 1, wherein the component (b1) comprises γ-methacryloxypropyl hepta( The structural unit of trifluoropropyl)-T8-silsesquioxane;

The component (b2) is a polydimethylsiloxane macromonomer having methacryl groups at both ends. The photopolymerizable coating composition according to claim 1, further comprising component (c): a fluorine-based surfactant. An article having a coating layer, comprising a coating layer composed of a cured product of the photopolymerizable coating composition described in any one of claims 1 to 3. A laminated film, which is a coating layer composed of a cured product of the photopolymerizable coating composition described in any one of claims 1 to 3, composed of thermoplastic polyurethane The substrate layer and the adhesive layer composed of pressure-sensitive adhesive are sequentially connected. A paint protection film, which uses the laminated film described in item 5 of the patent application.

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